DE2047248A1 - Filaments and films made from acrylonitrile copolymers free of vacuoles - Google Patents

Description

FARBENFABRIKEN BAYER AG _{on / no / o} LEVERKUSEN- B «yerwerk

Sdt / Ne

2 4th SEP. 1970

Patent department

Threads and films made from acrylonitrile copolyiiierisates free of vacuoles

The invention of vacuoles free fibers and films from acrylonitrile copolymers containing 20 to 80 wt - contain "/ o of vinylidene chloride and / or vinyl chloride..

In the production of threads or films from copolymers of acrylonitrile with vinylidene chloride and / or vinyl chloride it has proven to be disadvantageous that the products obtained contain vacuoles. The vacuoles cause the Threads and films appear more or less dull when treated with water or steam at an elevated temperature will. Inevitably, molded articles such as threads are exposed to the action of hot water or in manufacturing processes Exposed to water vapor, e.g. threads during drawing and crimping, the yarns obtained from them, e.g. during dyeing processes and finished fabrics when washing and ironing. The matting caused by vacuoles is uncontrollable and obvious strongly dependent on the external conditions, i.e. the intensity and the temperature with which the water flows Action arrives, so that the pieces made of threads or films show an uneven appearance of the goods.

It has now been found that in the case of threads or films made from copolymers of acrylonitrile with 20 to 80 wt .- ^ vinylidene chloride and / or vinyl chloride the formation of vacuoles

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can be significantly reduced or even avoided entirely, when you consider the spinning solutions from the Acrylonitrilcopolynicrisaten and organic solvents, homopolymers of vinylmethylformamide or copolymers of vinylmethylformamide with up to 90 mol $ vinyl esters or acrylic acid esters in an amount of 0.5 to 20 wt .- ^, based on the copolymer mixed from acrylonitrile and vinylidene chloride and / or vinyl chloride.

The invention accordingly relates to threads and films made from polymer mixtures which are free from vacuoles Mixtures of

a) 99> 5 to 80 wt .- ^ of a copolymer of Aerylni trils with 20 to 80 wt .- ^ vinylidene chloride and / or vinyl chloride and

b) 0.5 to 20 wt .- ^ of a homopolymer of methyl vinyl formamide or its copolymers with up to 90 mol. $ of a vinyl ester or an acrylic acid ester.

The vinyl esters of the lower aliphatic fatty acids are preferred as vinyl esters, and the esters of acrylic acid with lower aliphatic alcohols, preferably C ₁ to C alcohols, are preferred as acrylic acid esters. The molecular weight of the homo- or copolymers added according to the invention can vary within wide limits. In general, polymers with K values (according to H. Fikentscher, Cellulosechemie 13 (1932) p. 58) between 2 and 100 are effective. Polymers with a K value of 25 to 40 are particularly favorable. The polymers of vinylmethylformamide can, for. B. manufactured according to DAS 1.246.248, a special manufacturing process is not claimed here. The monomeric IT-vinylmethylformamide is obtainable, for example, according to DAS 1.235.983 from N- (α, -methoxyethyl) -N- methylformamide obtained according to DAS 1.273.533.

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Suitable organic solvents which can be used in the preparation of the spinning solutions of the mixtures according to the invention are the customary polar solvents for polyacrylonitrile, such as dimethylformamide, dimethylacetamide, ethylene carbonate, Y ~ -butyrolactone, dimethyl sulfoxide, hexamethylphosphoric triamide; in addition, acetone and tetrahydrofuran, for example, can also be used as solvents.

The testing of homopolymers and copolymers as stabilizers against vacuole formation is carried out as follows:

Films of the acrylonitrile copolymers with vinylidene g chloride and / or vinyl chloride, or from the mixture of the acrylonitrile copolymer A) with the copolymer b) are treated to four times according to the scheme after stretching:

1) one hour boil in water at 1oC ³ G 2) after one hour to dry at 5O ⁰ C 3) 20 minute anneal at 14O ⁰ C 4.) one hour boil in water at 100 ⁰ C and dry for 30 minutes at 50 ⁰ C

When testing a film made from a copoly-

merisat a) without addition of b): ™

Treatment level Appearance of the film 1 whitish cloudy 2 whitish cloudy 3 clear 4th whitish cloudy

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If an additive is effective as a substance stabilizing against vacuoles, then already at levels 1 and 2, but especially after completing stage 4 of the treatment regimen, films are significantly clearer. As well as films threads behave.

The addition of the claimed copolymers also affects other properties of the underlying copolymer from acrylonitrile and vinylidene chloride and / or vinyl chloride. Due to the increased sheen of threads and Filming is z. B. in the case of coloring, the color tone is more brilliant and the color intensity appears more intense.

In the following examples, parts by volume are related to parts by weight as liters are related to kg.

The K-value was determined according to Fikentscher, Cellulosechemie, 13 (1932), 58.

Production of N-vinyl-N-methylformamide polymers.

In 30 parts by volume of tert-butanol are 5 parts by weight N-vinyl-N-methylformamide was heated with 0.1 parts by weight of azobisisobutyronitrile in a nitrogen atmosphere with stirring to 80 ⁰ C. After a short time, the polymer begins to separate out in the form of white flakes, which multiply continuously, so that a fine-grained precipitate permeates the entire liquid and the stirrer is expediently stopped. After a total of eight hours of heating, the product is poured into petroleum ether and washed out with petroleum ether; A total of 100 parts by volume of petroleum ether are consumed. After drying at 40 ^° C. in vacuo, the homopolymer is obtained in a yield of 9456 with a K value of 23, measured in dimethylformamide with the addition of

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1 $ sodium sulfate as a solvent at 25 ¹¹ C.

In 80 parts by volume of tert-butanol, 8.5 parts by weight of N-vinyl-N-methylforroamid with 8.6 parts by weight of vinyl acetate and 0.5 parts by weight of azobisisobutyronitrile was heated in a nitrogen atmosphere with stirring to 80 ⁰ C. . The mixture becomes viscous after a short time and maintained for 9 hours at 80 ⁰ G with stirring. Most of the polymer precipitates out on cooling. For work-up is again heated after 24 hours at 8O ⁰ C and precipitated by stirring in petroleum ether, washed with petroleum ether and dried in vacuo at 40 ⁰ C dried. The yield is $ 77, the K value, measured in dimethylformamide, is 25

In 80 volume of tert-butanol, 8.5 parts by weight of N-vinyl-N-methylformamide with 8.6 parts by weight Acrylsäuremethy! Ester and 0.5 parts by weight of azobisisobutyronitrile in a nitrogen atmosphere with stirring to 80 ⁰ C heated. After about 45 minutes, the batch becomes cloudy and the polymer increasingly begins to separate out. After nine hours of warming to 80 ^° C., work-up is carried out as in Example 2. A product with a K value in dimethylformamide of J51 is obtained in a yield of 85 °.

example 1

From a copolymer of 65 parts by weight of acrylonitrile, 35 parts by weight of vinylidene chloride and 1 part by weight of methacrylic yloylaminobenzene-benzene-disulfonimide, with and without 2.4, 7.5 and 10% by weight of the under A ) described homopolymer from N-vinyl-N-methylformamide iO $ ige solutions in dimethylformamide. The resulting solid, dried at 5O ⁰ C films into strips of 10 mm width

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Ratio 1: 4 stretched, boiled for one hour in water, for one hour at 50 ⁰ C dried 20 minutes uei annealed HO ⁰ C, again boiled for one hour in water, and half an hour at 50 ⁰ C dried. The matting is assessed as follows:

Films cooked moist for an hour

dried

at 14i) ° 0
annealed

Boiled for an hour and p; e dries for 30 minutes

without addition: cloudy cloudy almost clear cloudy with 2? 6 slightly cloudy almost clear clear clear with \ i <> almost clear clear clear clear at $ 7.5 clear clear clear clear with 1096 clear clear clear clear

So it is by adding $ 2 of the homopolymer already achieved a strong effect.

Example 2

From a copolymer of 65 parts by weight of acrylonitrile, 35 parts by weight of vinyl chloride and 1 part by weight of methacryloylaminobenzene-benzene-disulfonimide, with and without 2, 4, 7.5 and 10 parts by weight of the 96 described under B) Copolymer of 1 mole of N-vinyl-N-methylformamide and 1 mole of vinyl acetate 10 $ solutions in dimethylformamide. The resulting solid, dried at 50 ⁰ C films into strips of 10 mm width in the ratio of 1: 4, boiled for one hour in water, for one hour at 50 ⁰ C dried, annealed 20 minutes at 140 ⁰ C, boiled wiederumjeine hour in water ^{and dried at 50 °} C. for half an hour. The matting is assessed as follows:

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Films boiled and dried for one hour

annealed at HO ^{0 C.}

boiled for an hour and dried for 30 minutes

without addition: cloudy cloudy almost clear very cloudy

with 2 $ slightly cloudy slightly cloudy clear cloudy

with $ 4 clear clear clear almost clear

with 7.5 ^ clear clear clear clear

with $ 10 clear clear clear clear

It is already through the addition of $ 2 of the copolymer a clear effect is achieved, which becomes even more pronounced when the dosage is further increased.

Example 3

From a copolymer of 65 parts by weight of acrylonitrile, 35 parts by weight of vinylidene chloride and 1 part by weight of methacryloylaminobenzene-benzene-disulfonimide, with and without 2, 4, 7.5 and 10% by weight of the under C) Copolymer described from 1 mole of N-vinyl-N-methyl-formamide and 1 mole of methyl acrylate produced 10 $ solutions in dimethylformamide. The resulting solid, dried at 5O ⁰ C films into strips of 10 mm width in the ratio of 1: 4, boiled for one hour in water, for one hour at 50 ⁰ C dried, annealed 20 minutes at 140 ⁰ C, again one hour in water ^{boiled and dried at 50 °} C. for half an hour. The matting is assessed as follows:

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Films boiled and dried for one hour

at HO ⁰ C
annealed

ei τα.- ·. Cooked for an hour and dried for 30 minutes

without addition: cloudy cloudy almost clear very cloudy with 2 $ slightly cloudy slightly cloudy clear slightly cloudy with $ 4 slightly cloudy almost clear clear almost clear with $ 7.5 clear clear clear clear with $ 10 clear clear clear clear

It is already through the addition of 2 $ 6 of the copolymer a clear effect is achieved, which increases with further increases in dosage.

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Claims (4)

Claims . Vacuole-free traps and films made from polymer mixtures, consisting of a mixture of: a) 99.5 to 80 wt .- ^ of a copolymer of acrylonitrile with 20 to 80 wt .- ^ vinylidene chloride and / or vinyl chloride and b) 0.5 to 20 wt .- ^ of a homopolymer of N-vinyl-N-methylformamide or its Copolymers with up to 90 mol # of a vinyl ester or an acrylic acid ester. 2. threads and films free of vacuoles according to claim 1, characterized in that component a) up to 5 wt .- ^, preferably 0.5 to 2 wt .- ^, one the mono-olefin compound imparting colorability with functional acidic and / or basic groups. 3. Free of vacuoles threads and films according to claim 1, characterized in that the component b) a K value (according to Fikentscher, Cellulosechemie 13 (1932), page 58) of 2 to 100. 4. A process for the production of threads and films which are free from vacuoles, characterized in that man a) 99.5 to 80 wt. - $> of a Copolyraerisates of acrylonitrile with 20 to 60 wt .- # vinylidene chloride and / or vinyl chloride and Le A 13 295 - 9 - 2098U / 1335 b) 0.5 to 20 wt .- ^ metbylformamid N-vinyl-N-a homopolymer, or its copolymers with up to 90 mole i "of a Vinylesters or acrylate mixed together in solution and processed into threads or films in the usual way. Le A 13 295 - 10 - 2098U / 1335